Polymerizing olefins



March* 23,1943. y E. E. STAHLY ETAL 2,314,458

POLYMERI Z ING OLEFINS Filed sept. so, 195e Patented Mar.v 23, 1943 ronmnmznvo oLEFrNs Eldon E. stably ana mns n. Johnson, anton Rouge, La., assignors to Standard Oil Development Company, a corporation of Delaware .Application september ao, 193s, serial No. 232,49

s claims. (ci. 19e- 10) This invention relates to improvements inthe process of4 polymerizing oleflns, vand pertains more particularly to the production of low boiling olefin polymers of motor 'fuel boilingy range.

It has heretofore been proposed to lform hydrocarbons within the motor fuel range byy polymerization of normally gaseous oleiins. The polymerization can be accomplished through the medium of various agencies well known in the art. For example, the polymerization can be accomplished by contacting the gaseous oleiins with polymerizing catalysts such as, for example, sulfuric acid, phosphoric acid, aluminum chloride, complex metal halidessuch as sodium aluminum chloride, zinc chloride, boron fluoride, certain highly active clays, synthetic gels and the like. Polymers ranging' from light -liquid motor'fuel constituents up to heavy solid or semi-solid products can be producedv from such gaseous olefins.

By properly regulating the polymerizing conditions, such as temperature, pressure,- type of catalyst. time of contact, oleilnv composition and other factors, the relative proportions `of the different polymers present in the ilnal product can be controlled within limits. For exa`mple, when It is o further more detailed object of this invention to provide a continuous processfor the productionv of -polymers boiling within the gasoline range in which the formation of undethe polymerizing zone will vary with the nature and concentration of the oleilns treated and the conditions maintained within Vthe polymerizing zone such as. for example, temperature, prespolymerizing isobutylene under low temperature conditions, such as below 10 C., employing boron fluoride asa catalyst, the resulting product may consist chiey of extremely high molecular weight Asolid or semi-solid polymers, whereas under higher temperatures employing sulfuric acid, phosphoricacid, activated clays, or the like, a product consisting principally of low molecular weight polymers of motor fuel boiling range, such as, for example, diisobutylene, may be obtained.

When operating the process to produce lowto provide a process which willresult in an increase in yield of polymers boiling within the desired range.

sure, nature .of catalyst, time of contact and other factors, each of which should. of necessity. be inter-dependently correlated with the others so-that as a practical matter it is not possible 4to state the specific amount of undesirable polymers which should be present in order to meet all conditions of operation. l

The minimum amount of'undesirable, polymers necessary to suppress further formation may -be readily determined by laboratory tests.

For example, the amount of undesirable. polymers' added to the polymerizing zone for vany i l given set of conditions may be progressively lncreased until the amount of undesirable higher boiling products appearing in the reaction products is not substantially greater' than the amount being charged into the polymerizing zone. Vitinother 'convenient method is to carry out the polymerization in the conventional manner separating the resulting products into a desired lower boiling fraction and an undesired higher boiling fraction, and continuously recycling the unde-k sired fraction to the polymerizing zone. When this is done, the undesired higher boiling polymers will accumulate or build up in the System until a point is reached where substantially no further undesirable polymers will -be formed.

" In its more specific aspect, the invention comprehends a continuous recycle operation of this nature.

The reaction conditions maybe varied over quite a wide range depending upon the types of reactants, catalysts, etc., that are employed. Temperatures ranging from between about 150 F. and about 600 F. are satisfactory for most reaction conditions and for most catalysts. It is The4 amount furie acid or other liquid as a catalyst.

sometimes advantageous, especially when it is desired to carry out a continuous reaction, to maintain the feed stock substantially in the liquid phase and to use elevated pressures so correlated with the particular temperatures employed as to attain this desired liquid phase operation. Pressures of from about 100 lbs/sq. in. up to about 1900 lbs./sq. in. may be employed. Likewise, particularly in continuous operations, the feed rate to the reactor may vary considerably. Suitable rates, however. range from vbetween about 30 and about 100 gallons of feed measured in the liquid phase per square foot of reactor cross-sectional area per hour.

Having thus described the general nature and the objects, the invention will be better understood from the more detailed description hereinafter in which reference will be made to the accompanying Adrawing which is a diagrammatic illustration of one form of an apparatus capable of carrying the invention into effect..

For illustrative purposes, there is shown in the accompanying drawing a diagrammatic illustration representing a process adapted topolymerize gases in liquid phase, employing sul- The process .may be readily adapted to use a solid or gaseous catalyst as well. vIt will be understood. however, that the invention in its broader aspects is not restricted to the particular type of polymerizing process illustrated in the accompanying drawing and described more in detail hereinafter.

Referring to the drawing, the olens to be polymerized. which may be a pure olefin or a mixture ofoleilns or a gas relatively rich in ole- 'fina such as, for example, gases resulting from the cracking of petroleum oil. after being sub- .Iected to a pressure sufficient-to convert said gas into a liquid. are introduced into the polvmerizing reaction chamber I through charging line 2. There is also introduced into the reaction chamber I a predetermined minimum amount of polymers of such oleilns boiling above those desired to be obtained as a'flnal product.- As shown. this product is introduced into the reaction chamber through line 3 which-merges with charge line 2. It will be understood. however. that such higher boiling polymer may be separately introduced into the polvmerizing chamber. These undesirable higher boiling oleilns may be formed in the process or obtained from 'an extraneous source as hereinafter described. The amount added is erating under these conditions, with a .refinery butane cut containing about isobutylene and about 20% normal butylepe, the amount of --undesired higher boiling polymers, combined with the fresh feed,- will be of the order of by weight.

The mixture of oleiln-containing liquid and. t undesired higher boiling polymers, introduced into the polymerizing chamber I, is dispersed into the acid by porous thimbles 4 or other suitable dispersing elements such as jets.' turbomixers or the like. so that the mixture is dispersed in finely divided state into the body of the acid contained within the reactor.

Reaction products from chamber I, containing some of the sulfuric acid entrained therein, pass overhead through line 5 to a cooling coil 6, and thence to a separator 1 in which the entrained acid separates from the reaction products. The

4sulfuric acid separated in chamber 1 is withdrawn therefrom and returned to the reaction chamber I through line 8. Fresh acid to make up for that lost in the process maybe introduced into line 8 thru inlet 8'.

Reaction products. together with the undesired high boiling polymers introduced into the polymerizing chamber, after separation from the acid in the separator 1, pass through line 9 to a heating coil I0 in which the products are heated to a temperature sufcient to vaporize polymers boiling within the motor fuel boiling range. Products from the heating coil I0 discharge into a fractionating tower II containing fractionating tion of the tower to collect condensate formed above said tray. This condensate is withdrawn from the tower through line I3. The tower temperature is controlled so that the desired motor fuel constituents are collected above the trapout I2 and withdrawn through line I3. The undesired higher boiling condensate collects in the bottom of the tower and is withdrawn through line Iii.

In accordance with the preferred embodiment of the invention, the undesired higher boiling polymers withdrawn from the fractionating tower tion of such undesired polymers is substantially suppressed.

Returning now to the fractionating tower I I, I

vapors remaining uncondensed therein are removed overhead through line I1. These, after being, compressed by. compressor I9 and/liquefied in cooling coil 20, may be recycled to the inlet of the reaction chamber through line I8,.for a part or Vall of the uncondensed vapors may be removed from the system-through line 2|. In cases where the fresh charging stock contains substantial quantities of saturated constituents,

the vapors withdrawn from the fractionating tower Il may be passed through suitable equipment, not shown, for removal of the saturated constituents before being returned to the polymerizing chamber if so desired. a

Recycle. line I4 is provided with a tap-off line I4' so that a portion or all of the undesired polymers collected in tower Il may be withdrawn from the system. yDuring operation, however.

. chamber so that the acid as well as the oleiins and undesired polymers are caused to be dispersed into the chamber through thimble or the like. To this end, the acid hydrocarbon mixture withdrawn from separator l through line 8 may be recycled through line 22 'and pump 23 to recycle line i4 when it merges with the recycle higher boiling polymer. Also, if desired, a part of the acid hydrocarbon mixture Withdrawn from the reactor through line 5 may be recycled through line 2l and pump 25 to give more intimate contact and better mixingof fresh feed and i reaction mixture.

In cases where a solid catalyst is used, the polymerization reactor I may be packed with such solid catalyst, or the catalyst may besupported on a series of trays mounted within the chamber. In place of a single reaction chamber, two or more chambers arranged in parallel may more of the chambers may be carrying out the process whereas the catalyst in other ofl the chambers is undergoing regeneration, thus providing for a continuous process in cases where solid catalysts are-used as well as where liquid catalysts are used.

The term polymerization as here employed is intended to mean any one of the following reactions or any combination thereof. First, the union of two or more molecules of a simple monomer such as, for example, the union of two molecules of isobutylene to form diisobutylene. Second, the union of two or more molecules of unlike monomers of the same molecular weight but of different structural formula such as, for example, the union of a -normal butylene with isobutylene. This reaction is often referred to as copolymerization. Third, the union of two or more molecules of unlike monomers ofdifferent molecular weights such as, for example, the union of propylene with butylenes. This reaction is often referred to as cross or heteropoly merization.

The invention has been found to be especially applicable to the copolymerization reaction and asians be used whereby the catalyst contained in oneor particularly to the copolymerization of normal and isobutylene.

The term undesired higher boiling polymers as herein employed is intended to mean polymers boiling above the final desired product. The

invention has been described with reference to the production of gasoline polymers. It will be understood, however, that in its broader aspects the invention comprehends the' production of other intermediate final products such as Diesel and lubricating oils. It will be understood that in producing the latter named products, theformed within the process.

mers formed in this case amountedto '10% by following examples may .be helpful, it being l understood that suchexamples are illustrative rather than limitative.

Example 1 A lrefinery C4 fraction containing about `13.17 of isobutylene, about 22.0% of normal butylen'cs and the remainder consisting principally of butanes together with small amounts of propane and pentanes was first admixed with 15% by volume of undesired higher boiling polymers consisting principally of butylene co-trilners together with a small amount of-heavier polymers. This mixture was charged into a reactor 51/2 inches in diameter and 1l feet in length containing sulfuric acid of '10% concentration through a jet having an internal diameter of 0.10 inch at a rate of 23.8 liters per hour. The reactor was maintained at a temperature of F.- and under a pressure of 200 pounds per square inch. Products were continuously withdrawn from the reactor and allowed to separate into an acid phase and an oil phase. 'I'he acid phase was continuously returned to the reactor. v

The oil phase was then heated and fractionated to ilrst liberate the spent C4 fraction from the polymers. into butylene dimers and polymers heavier than dimers.

'I'he amount of trimers and heavier so recovered amounted to about 15% of the refinery C4 fraction by volume which corresponded to the amount of such polymers combined with the C4 fraction before being introduced into the reactor, thus showing that no additional trimer or heavier polymers were formed during the process. The yield of polymers formed inthe process amounted to 66.3% by weight of the' total C4 unsaturates contained in the feed stock. 'I'he dimer product so produced consisted chiefly of the co-dimer of butylene and isobru'tylene, together with a small amount of diisobutylene.

The process was repeated under substantially the same conditions outlined in Example 1,

The polymers were then segregated except that the amount of butylene trimer and heavier initially combined with the C4 fraction amounted to 10% by volume rather than 15% as in Example l. In this case, the final product,

excluding the trimers and heavier initially added to the reactor, consisted of 96% butylene dimers comprising chieiiy co-dimers, and 4% butylene trimers and heavier hydrocarbons. The total yield of polymers formed amounted to 68.8% by weight of the C4 unsaturates contained in the feed stock. e

Example 3 Theprocess set forth in Example 1 was repeated under substantially the same conditions, except that no undesirable higher boiling butylene trimers were combined with the feed stock to the reactor. In this case, 15% of butylene trimers and heavier was recovered from the process, thus showing that in the absence of the butylene trimers 15% of undesirable butylene trimers was The yield of poly- Weight of the unsaturates contained in the feed stock, of which, as already mentioned, 15% conis'isted of undesirable butylene trimers and heav- From the above examples, it will be'seen that when operating under conditions set forth therein, it is necessary to combine a minimum of about with the fresh feed during the operation.

15% by volume of butylene trimers into the feed stock to suppress further formation of such trimers during the process. While 15% by volume is the minimum percentage when operating under the conditions set forth in the examples, it will be understood that it is not minimum under all conditions of operation. The minimum percentage of undesired higher boiling polymers to r weight of such butylene trimer or heavier to the charge.

While it will be clear from the above examples that when operating under the conditions set forth therein it is necessary to combine at least about 15% of butylene trimers or heavier `to suppress further formation of such trimers in the reaction, it should be mentioned that the presence of higher percentages of such trimers will not adversely affect the reaction but, in fact, increase the total yield of dimers resulting from the process.

From the following examples, it will be apparent that the invention is not restricted to a process employing hot sulfuric acid as a catalyst.

'Example 4 A C4 fraction of the composition set forth in Example l was first combined with about 8% by volume of butylene trimers and heavier, and this mixture was charged into a reactor 2.5 inches in diameter and 5 feet in length packed with a solid catalyst consisting of phosphoric acid supported on Kieselguhr. The reactor was operated at a temperature of 290'F. and under a pressure of 550 pounds per square inch. The final product consisted of 95% dimers comprising chiefly vcodimers and 5% butylene trimers and heavier consisting principally ofAco-trimers, excluding the original 8% co-trimers added to the first charge.

Ezample 5 The process set forth in Example 4 was repeated under substantially the same conditions except that no butylene trimers were combined In this case, the polymer products comprised 88% dimers consisting principally of co-dimers of normal and isobutylene and 12% of trimers andheavier. The yield of polymers in this case amounted to 60% of the unsaturates contained in the feed stock.

Ezarnple A C4 fraction oi' the composition set forth vin Example 1 was first combined with 8% by volume of butylene trimers and the resulting mixture was charged into the reactor similar to that employed in Examples 4 and 5, but containing activated clay in pill form of the type known in the trade as- Super Filtrol. The reactor was maintained under a temperature of 300 and under a pressure of 550 pounds per square inch. In this case, theresulting polymers amounted to 41.6% of the total C4 unsaturates contained in the feed. The polymer product consisted of about 57% dimers and 43% trimers and heavier after deduction of the original 8% combined with the feed.

' Example 7 'I'he process set forth in Example 6 was'repeated, except that no trimers were combined with the feed stock prior to introduction into the reactor. formed amounted to 46% of the unsaturates contained in the feed stock and 50% ofthe polymer product consisted of dimers and 50% trimers and heavier.

It will be apparent from the above examples that the presence of the trimer in the reactor tends to suppress the formation of further trimers and that by combining a sufficient quantity of trimer, further formation of such trimer may be virtually suppressed. v

In the appended claims, the words trimer and heavier polymers" are intended to include trimer products whether they be co-trimers, trimers, or cross-trimers.

Having described the preferred embodiment of theinvention, and given speci'c examples, it will be understood that the invention embraces such other variations and modifications as come within the spirit and scope thereof. It will be further understood that it is not our intention to unnecessarily restrict .the invention or to deduct any novel features thereof.

We claim:

1. In the process of catalytically polymerizing normally gaseous monolens to liquid hydrocarbons of predetermined boiling range and wherein the final product is fractionated into a lighter fraction, a middle fraction and a heavier fraction, substantial quantities of the higher vboiling products being Inormally formed in the process, the improvement which comprises recycling substantially all of such higher boiling polymers contained in the reaction product to the polymerization zone in amounts substantially equal to the amounts normally formed in the reaction andat the same rate atwhich they are formed in and removed from the said reaction.

2. In a process for the conversion of low boiling oleflns into higher boiling hydrocarbons of pre-v determined boiling range wherein said olens are passedthrough a reaction zone containing a catalyst maintained under conditions capable of effecting said conversion, and the products from said reaction zone fractionated to separate a product of said predetermined boiling range and wherein reaction products boiling above the desired range are normally formed Ain the process, the improvement which comprises continuously introducing into said reaction zone only a quantityof said last named higher boiling reaction products sufficient to substantially completely suppress the formation of said products during the process.

3. A process which comprises polymerizing a liquid mineral acid polymerizing catalyst, fractionating the resulting polymer mixture to separate the same into a fraction boiling within the desired motor fuel boiling r'ange and a heavier fraction, and returning substantially all of said heavier fraction to the polymerizing zone in an amount substantiallyfequal to the amount nor- `mally formed in the relation and at the rate at In this case, the amount of polymers which the heavier fraction is formedin said reaction.

4. A process which comprises dispersing al liquefied normally gaseous hydrocarbon mixture containing olens into a liquid polymerizing catalyst within a reaction zonev maintained under conditions which will polymerize said olefins into higher boiling polymers, continuously' withdrawing from said reaction zone a mixture of reaction products and a liquid catalyst, removing the liquid catalyst from the reaction products and, `returning thesame to the reaction zone, irac-Y tionatlng the reaction products to segregate a fraction of desired predetermined boiling range and introducing into said reaction zone only that quantityof polymers of said oleflns boiling above the desired boiling range sufficient to substantially prevent formation of said last named polymers in the process.

5. In process as defined in claim 4, the further improvement which comprises combining a portion of the mixture Aof reaction products and lliquid catalystk with said refinery gas prior to dispersing the same 'into said liquid polymerizing catalyst. y v 6. The process as defined in claim'4 in which the liquid catalyst is sulphuric acid. l

7. In the process of polymerizing a refinery gas containing a substantial quantity of normal and isobutylenes at a temperature between about F. and about 600 F. and at a pressure y between about 100 and about 1900 lbs/sq. in. by passing the reactants over a polymerizlng catalyst, followed by separation of the polymers boiling within the motor fuel boiling range from heavier polymers, the improvement which comprises returning to the original polymerizing reaction chamber substantially all of said heavier polymers in the amount and at the rate at which they are formed in the reaction.

'in a polymerizing zone maintained at about F.,.and under about 200 1bs./sq. in. and containing sulphuric acid of about 70% concentration, continuously passing the reacted mixture vinto a fractionating tower, continuously separating the fraction boiling within the motor fuel boiling range and continuously returning all of the heavier polymer bottoms from the fractionation to\ the feed line tothe polymerizing zone.

I ELDON E. vSTAHLY.

FRANK B. JOHNSON. 

